Method of manufacturing silicon carbide semiconductor device

ABSTRACT

A method of manufacturing a silicon carbide semiconductor device includes forming a first silicon carbide layer of a first conductivity type on a front surface of a silicon carbide semiconductor substrate. A thermal oxidation film is formed on a surface of a base body including the first silicon carbide layer. The thermal oxidation film is subsequently removed using a solution containing hydrofluoric acid. The base body is washed with a mixture of ammonia water and a hydrogen peroxide solution, a mixture of hydrochloric acid and a hydrogen peroxide solution, and a dilute hydrofluoric acid. The base body is held at temperature of 700 degrees C. to 1700 degrees C., and an insulating film is deposited on the base body.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 15/938,481, filed on Mar. 28, 2018, and claims the benefit ofpriority of the prior Japanese Patent Application No. 2017-079316, filedon Apr. 12, 2017, the entire contents of which are incorporated hereinby reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

Embodiments of the invention relate to a silicon carbide semiconductordevice and a method of manufacturing a silicon carbide semiconductordevice.

2. Description of the Related Art

A silicon carbide (SiC) semiconductor material has a high dielectricfield strength and therefore, use of silicon carbide as a material innext generation power semiconductor devices having low loss is expected.Silicon carbide semiconductor devices having various types of structuressuch as Schottky barrier diodes, metal oxide semiconductor field effecttransistors (MOSFET), etc. have been developed. In general, amongMOSFETs, a trench type having a gate electrode in a trench that isnearly vertical to a surface of a substrate enables the cell density perunit area to be increased more than the cell density per unit area in aplanar type having a gate electrode on the surface of the substrate andthus, the trench type enables the current density to be increased anddemands for large current to be met.

In fabrication (manufacturing) processes of these silicon carbidesemiconductor devices, processes similar to those for a silicon (Si)semiconductor device are often used because of the ease of applyingknowhow and manufacturing equipment. In the cleaning process, wetcleaning is applied using a strong acid and highly basic solution(so-called RCA) combining a mixture of ammonia (NH₃) water and ahydrogen peroxide solution (H₂O₂) (Standard Clean 1 (SC1)), a mixture ofhydrochloric acid (HCl) and a hydrogen peroxide solution (Standard Clean2 (SC29), and a dilute hydrofluoric acid (HF) (for example, refer toJapanese Laid-Open Patent Publication No. 2012-4270).

In a trench silicon carbide semiconductor device, formation of an oxidefilm having a uniform thickness on an inner surface of the trench isnecessary and therefore, a deposited film such as that formed by a hightemperature oxide (HTO) using silane gas is used rather than an oxideformed by thermal oxidation. Further, as a surface processing method ofa silicon carbide semiconductor substrate, a technique has beendisclosed in which etching is performed by a plasma process and usinghydrogen (H₂) (for example, refer to Japanese Patent No. 3733792 andJapanese Laid-Open Patent Publication No. H11-186256).

SUMMARY OF THE INVENTION

According to an embodiment of the present invention, a silicon carbidesemiconductor device includes a silicon carbide semiconductor substrateof a first conductivity type; a first silicon carbide layer of the firstconductivity type provided on a front surface of the silicon carbidesemiconductor substrate; and an insulating film selectively provided ona surface of the first silicon carbide layer. No fluorine or chlorine isdetectable in the insulating film, at a boundary layer of the insulatingfilm and the first silicon carbide layer, or at the surface of the firstsilicon carbide layer where the insulating film is provided.

According to an embodiment of the present invention, a silicon carbidesemiconductor device includes a silicon carbide semiconductor substrateof a first conductivity type; a first silicon carbide layer of the firstconductivity type provided on a front surface of the silicon carbidesemiconductor substrate; a second silicon carbide layer of a secondconductivity type selectively provided in a first surface of the firstsilicon carbide layer, the first surface opposite a second surface ofthe first silicon carbide layer facing the silicon carbide semiconductorsubstrate; and a gate insulating film provided on a surface of thesecond silicon carbide layer. No fluorine or chlorine is detectable inthe gate insulating film, at a boundary layer of the gate insulatingfilm and the second silicon carbide layer, or at the surface of thesecond silicon carbide layer where the gate insulating film is provided.According to an embodiment of the present invention, a silicon carbidesemiconductor device includes a silicon carbide semiconductor substrateof a first conductivity type; a first silicon carbide layer of the firstconductivity type provided on a front surface of the silicon carbidesemiconductor substrate; a second silicon carbide layer of the firstconductivity type selectively provided in a first surface of the firstsilicon carbide layer, the first surface opposite a second surface ofthe first silicon carbide layer facing the silicon carbide semiconductorsubstrate; a third silicon carbide layer of a second conductivityselectively provided on a first surface of the second silicon carbidelayer, the first surface of the second silicon carbide layer opposite asecond surface of the second silicon carbide layer facing toward thefirst silicon carbide layer; a trench at least penetrating the thirdsilicon carbide layer and reaching the second silicon carbide layer; anda gate insulating film provided on a surface of the trench. No fluorineor chlorine is detectable in the gate insulating film, at a boundarylayer of the gate insulating film and the second silicon carbide layer,or at the surface of the second silicon carbide layer where the gateinsulating film is provided.

In the embodiments, no fluorine or chlorine is detectable means aconverted concentration of fluorine and chlorine is less than 1×10¹⁷atoms/cm³.

In the embodiments, no fluorine or chlorine is detectable means aconverted concentration of fluorine and chlorine by Time Of FlightSecondary Ion Mass Spectrometry is less than 1×10¹⁷ atoms/cm³.

According to an embodiment of the present invention, a method ofmanufacturing a silicon carbide semiconductor device includes forming afirst silicon carbide layer of a first conductivity type on a frontsurface of a silicon carbide semiconductor substrate; forming a thermaloxidation film on a surface of a base body including the first siliconcarbide layer; removing the thermal oxidation film by a solutioncontaining hydrofluoric acid; washing the base body with a mixture ofammonia water and a hydrogen peroxide solution, a mixture ofhydrochloric acid and a hydrogen peroxide solution, and a dilutehydrofluoric acid; holding the base body at a temperature of 700 degreesC. to 1000 degrees C. in a reduced-pressure atmosphere; and depositingan insulating film on the base body.

According to an embodiment of the present invention, a method ofmanufacturing a silicon carbide semiconductor device includes forming afirst silicon carbide layer of a first conductivity type on a frontsurface of a silicon carbide semiconductor substrate; forming a thermaloxidation film on a surface of a base body including the first siliconcarbide layer; removing the thermal oxidation film by a solutioncontaining hydrofluoric acid; washing the base body with a mixture ofammonia water and a hydrogen peroxide solution, a mixture ofhydrochloric acid and a hydrogen peroxide solution, and a dilutehydrofluoric acid; holding the base body at a temperature of 700 degreesC. to 1000 degrees C. in a hydrogen atmosphere; and depositing aninsulating film on the base body.

According to an embodiment of the present invention, a method ofmanufacturing a silicon carbide semiconductor device includes forming afirst silicon carbide layer of a first conductivity type on a frontsurface of a silicon carbide semiconductor substrate; forming a thermaloxidation film on a surface of a base body including the first siliconcarbide layer; removing the thermal oxidation film by a solutioncontaining hydrofluoric acid; washing the base body with a mixture ofammonia water and a hydrogen peroxide solution, a mixture ofhydrochloric acid and a hydrogen peroxide solution, and a dilutehydrofluoric acid; holding the base body at temperature of 700 degreesC. to 1700 degrees C. in a mixed gas atmosphere containing hydrogen andsilane; and depositing an insulating film on the base body.

Objects, features, and advantages of the present invention arespecifically set forth in or will become apparent from the followingdetailed description of the invention when read in conjunction with theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a part of a configuration of asilicon carbide semiconductor device according to a first embodiment;

FIGS. 2, 3, and 4 are cross-sectional views of the silicon carbidesemiconductor device according to the first embodiment duringmanufacture;

FIG. 5 is a graph of surface analysis results of the silicon carbidesemiconductor device according to the first embodiment;

FIG. 6 is a cross-sectional view of the silicon carbide semiconductordevice according to a second embodiment;

FIGS. 7, 8, and 9 are cross-sectional views of the silicon carbidesemiconductor device according to the second embodiment duringmanufacture;

FIG. 10 is a cross-sectional view of the silicon carbide semiconductordevice according to a third embodiment; and

FIGS. 11, 12, 13, 14, and 15 are cross-sectional views of the siliconcarbide semiconductor device according to the third embodiment duringmanufacture.

DETAILED DESCRIPTION OF THE INVENTION

Problems related to the conventional techniques will be discussed. Whilehydrofluoric acid is widely used, it has been reported that when used onthe surface of the silicon carbide semiconductor material, fluorine (F),which is a cleaning liquid component, has a residual property, forexample, refer to Okamoto, Ryota, et al, “Atomic-scale analysis of4H—SiC (0001) surface after wet-chemical preparations”, 2006 JapanSociety for Precision Engineering, Autumn Meeting Presented PapersCollection, pp. 539 to 540). Further, the inventors found that when RCAcleaning is used, chlorine and fluorine remains on the surface of thesilicon carbide semiconductor material. In particular, it was found thatin a trench silicon carbide semiconductor device, cleaning solutionand/or rinsing solution in the trenches cannot be sufficientlycirculated, whereby fluorine and chlorine from inside the trenches tendsto be detected at higher concentrations than outside the trenches.Fluorine and chlorine were further detected from trench side surfacesconstituting channel surfaces.

Further, since a high-temperature oxide film is used as an oxide film onthe inner surface of the trenches, elements such as residual fluorine onthe trench surface tend to easily remain at an interface of the trenchsurface and the deposited film. It is presumed that these elements arenot only taken into the silicon carbide of the channel part and the gateoxide film by heat treatment at a subsequent process but also are takeninto the passivation film of the element outer peripheral part, wherebyan impurity state is formed.

Further, in a method using plasma as a surface processing method, it ispresumed that not only the impurity of the surface of the siliconcarbide but also the silicon carbide itself is removed by physicalimpact, forming dangling bonds, vacancies, etc., and an interface state.Further, with heat treatment in a hydrogen atmosphere as a surfaceprocessing method, it is presumed that rearrangement of the constituentelements of the silicon carbide occurs due to the temperature, danglingbonds and vacancies are formed by insufficient mobility, and aninterface state is formed.

It is presumed that due to these impurities of fluorine and chlorine aswell as the impurity state and the interface state, carrier mobility ofthe silicon carbide semiconductor device decreases, leading to anirregular decrease of the breakdown voltage.

Embodiments of a semiconductor device and a method of manufacturing asemiconductor device according to the present invention will bedescribed in detail with reference to the accompanying drawings. In thepresent description and accompanying drawings, layers and regionsprefixed with n or p mean that majority carriers are electrons or holes.Additionally, + or − appended to n or p means that the impurityconcentration is higher or lower, respectively, than layers and regionswithout + or −. Cases where symbols such as n's and p's that include +or − are the same indicate that concentrations are close and therefore,the concentrations are not necessarily equal. In the description of theembodiments below and the accompanying drawings, main portions that areidentical will be given the same reference numerals and will not berepeatedly described. Further, in the present description, when Millerindices are described, “−” means a bar added to an index immediatelyafter the “−”, and a negative index is expressed by prefixing “−” to theindex.

A semiconductor device according to the present invention will bedescribed using, as an example, a silicon carbide semiconductor devicefabricated using silicon carbide (SiC) as a wide bandgap semiconductormaterial. The silicon carbide semiconductor device will be describedtaking a silicon carbide semiconductor Schottky barrier diode as anexample. FIG. 1 is a cross-sectional view of a part of a configurationof the silicon carbide semiconductor device according to a firstembodiment.

As depicted in FIG. 1, in the silicon carbide semiconductor deviceaccording to the first embodiment, an n-type silicon carbide layer(first silicon carbide layer of the first conductivity type) 1 isprovided on a first main surface, for example, (0001) plane (Si face),of an n⁺-type silicon carbide semiconductor substrate (silicon carbidesemiconductor substrate of a first conductivity type) 100.

The n⁺-type silicon carbide semiconductor substrate 100 is a siliconcarbide single-crystal substrate doped with an n-type impurity such asnitrogen (N). The n-type silicon carbide layer 1 is a low-concentrationn-type drift layer doped with an n-type impurity such as nitrogen. Animpurity concentration of the n-type silicon carbide layer 1 is lowerthan an impurity concentration of the n⁺-type silicon carbidesemiconductor substrate 100. A thickness of the n-type silicon carbidelayer 1 varies according to the device breakdown voltage and a thicknessfrom about 3 μm to 100 μm is used.

In a first main surface of the n-type silicon carbide layer 1 (firstsurface of the n-type silicon carbide layer 1 opposite a second surfacethereof, the second surface facing the n⁺-type silicon carbidesemiconductor substrate 100), a p-type ion implant layer 4 forincreasing the breakdown voltage is provided. Further, in an edgetermination structure region in an outer periphery, a p-type ion implantlayer (not depicted) is provided, and an edge termination structure suchas a junction termination extension (JTE) structure, a guard ringstructure, etc. is formed. In an outer periphery of the p-type ionimplant layer, a channel stopper 16 is provided.

Further, an insulating film 9 is provided on a surface of the n-typesilicon carbide layer 1. Here, before formation of the insulating film9, an impurity (fluorine, chlorine) of the n-type silicon carbide layer1 is removed by the method of manufacturing as described in detailhereinafter. Therefore, the impurity (fluorine, chlorine (Cl)) is notdetected in the insulating film 9, or in a boundary layer of theinsulating film 9 and the n-type silicon carbide layer 1, or from thesurface of the n-type silicon carbide layer 1 where the insulating film9 is provided.

In a contact hole of the insulating film 9, a contact (Schottky barriercontact) electrode 12 is provided. The contact electrode 12 is incontact with the n-type silicon carbide layer 1 and the p-type ionimplant layer 4, via the contact hole opened in the insulating film 9.On the contact electrode 12, an electrode pad 14 is provided.

On a second main surface (the second surface opposite the first mainsurface on which the n-type silicon carbide layer 1 is formed) of then⁺-type silicon carbide semiconductor substrate 100, a rear electrode 13and a rear electrode pad 15 are provided.

The method of manufacturing the silicon carbide semiconductor deviceaccording to the first embodiment will be described taking, as anexample, a case in which a silicon carbide semiconductor Schottkybarrier diode is fabricated. FIGS. 2, 3, and 4 are cross-sectional viewsof the silicon carbide semiconductor device according to the firstembodiment during manufacture. First, the n⁺-type silicon carbidesemiconductor substrate 100 doped with nitrogen is prepared. Next, onthe n⁺-type silicon carbide semiconductor substrate 100, the n-typesilicon carbide layer 1 doped with nitrogen is formed by epitaxialgrowth.

Next, an oxide film mask for ion implantation is formed byphotolithography and etching, and the p-type ion implant layer 4 isselectively formed in a surface layer of the n-type silicon carbidelayer 1 by ion implantation. In this ion implantation, for example, adose may be set so that an impurity concentration of the p-type ionimplant layer 4 is from 1×10¹⁶/cm³ to 1×10²⁰/cm³. Further, an ionimplantation depth of the p-type ion implant layer 4 may be at maximumabout 0.7 μm, which enables recovery of crystal defects by heattreatment.

Next, an oxide film mask for ion implantation is formed byphotolithography and etching, and a p-type ion implant layer (notdepicted) is further provided selectively in the edge terminationstructure region by ion implantation. In this ion implantation, forexample, the edge termination structure such as a JTE structure or guardring is formed to have an implantation depth of about 0.7 μm and animpurity concentration of about 1×10¹⁶/cm³ to 1×10¹⁹/cm³.

Next, an oxide film mask for ion implantation is formed byphotolithography and etching, and the channel stopper 16 is selectivelyformed by ion implantation. In the ion implantation, an n-type region isformed by implanting phosphorus (P) ions or nitrogen ions. A p-typeregion is formed by implanting aluminum ions. The structure formed up tohere is depicted in FIG. 2.

Next, the n⁺-type silicon carbide semiconductor substrate 100 issubjected to activation annealing at a temperature of about 1700 degreesC. and then, a sacrificial oxide film (not depicted) is formed on asurface of a base body that includes the n-type silicon carbide layer 1formed on the n⁺-type silicon carbide semiconductor substrate 100. Next,the sacrificial oxide film is removed by hydrofluoric acid. As a result,a damage layer and impurities such as metal on the surface of the n-typesilicon carbide layer 1 are removed. Next, the base body is cleaned (RCAcleaning) using a mixture of ammonia water and a hydrogen peroxidesolution, a mixture of hydrochloric acid and a hydrogen peroxidesolution, and a dilute hydrofluoric acid.

The surface of the base body subjected to the RCA cleaning is covered byfluorine, chlorine, a hydroxyl group (—OH), etc. and therefore, when asilicon oxide film is formed by thermal oxidation, fluorine and chlorinetends to be taken in more in the oxide film rather than a boundaryportion. These elements form an impurity state in the insulating filmand in particular, cause problems such as decreases in the breakdownvoltage in a reliability test.

As method of removing these elements, in the first embodiment, a processis performed in which the base body is held at a temperature of 700degrees C. to 1000 degrees C. in a reduced-pressure atmosphere, wherebythe elements are eliminated from the surface. Further, a process isperformed in which the base body is held at a temperature of 700 degreesC. to 1000 degrees C. in a hydrogen atmosphere, whereby fluorine andchlorine of the surface are eliminated as hydrogen fluoride and hydrogenchloride (HCl) and the silicon carbide surface is hydrogen terminated.Further, a process is performed in which the base body is held at atemperature of 700 degrees C. to 1700 degrees C. in a mixed gasatmosphere including hydrogen and silane (SiH4), whereby fluorine andchlorine are eliminated as hydrogen fluoride and hydrogen chloride andsurface diffusion is utilized to reduce vacancies, etc. of the siliconcarbide surface while the silicon carbide surface is hydrogenterminated. These processes may all be performed. At least one of theprocesses suffices to be performed. After at least one of theseprocesses is performed, the insulating film 9 is formed by thermaloxidation or a deposition method. The structure formed up to here isdepicted in FIG. 3.

In the case where the base body is held in a reduced-pressureatmosphere, although the elimination of fluorine and chlorine isfacilitated by setting the temperature to 700 degrees C. or higher,oxidation of the surface of the n-type silicon carbide layer 1 (firstn-type silicon carbide layer) progresses and therefore, the temperaturemay be set to be 1000 degrees C. or less. The temperature may be furtherset to a range from 750 degrees C. to 900 degrees C. When the base bodyis held in a hydrogen atmosphere, although setting the temperature to700 degrees C. or higher converts fluorine and chlorine of the surfaceto hydrogen fluoride and hydrogen chloride and facilitates elimination,the temperature may be set to be 1000 degrees C. or less to suppressetching of the surface of the n-type silicon carbide layer 1. Thetemperature may be further set to a range from 800 degrees C. to 900degrees C. When a mixed gas atmosphere including hydrogen and silane isused, the silane concentration may be from 0.1 to 1.0 volume %. When thesilane concentration is higher than this concentration, the depositionof silicon (Si) to the surface of the n-type silicon carbide layer 1clearly appears. The removal of fluorine and chlorine is observed from700 degrees C. or higher, and to suppress excess surface diffusion suchas step bunching formation, the temperature may be 1700 degrees C. orless. The temperature range may be from 1300 degrees C. to 1600 degreesC. Table 1 shows TOF-SIMS analysis results of peak concentrations ofchlorine and fluorine for each of the processes. An intensity of asample for which preprocessing was not performed is assumed to be

TABLE 1 600° 700° 800° 900° 1000° 1100° 1200° 1300° 1400° 1500° 1600°1700° 1800° C. C. C. C. C. C. C. C. C. C. C. C. C. LOW FLUORINE 1.000.80 0.50 0.40 0.30 0.20 — — — — — — — PRESSURE CHLORINE 0.95 0.50 0.300.25 0.20 0.15 — — — — — — — ATMOSPHERE HYDROGEN FLUORINE 1.00 0.70 0.450.35 0.28 0.20 0.18 — — — — — — ATMOSPHERE CHLORINE 0.80 0.40 0.20 0.150.12 0.10 0.10 — — — — — — HYDROGEN/ FLUORINE 1.00 0.70 0.30 0.25 0.230.20 0.18 0.10 0.10 0.08 0.08 0.07 0.06 SILANE CHLORINE 0.80 0.40 0.180.16 0.15 0.10 0.10 0.10 0.10 0.08 0.08 0.07 0.06 MIXED GAS ATMOSPHERE

Next, a contact hole is opened in the insulating film 9 and the contactelectrode 12 is formed. The contact electrode 12 is in contact with then-type silicon carbide layer 1 and the p-type ion implant layer 4, viathe contact hole opened in the insulating film 9. On the contactelectrode 12, the electrode pad 14 is formed. The structure formed up tohere is depicted in FIG. 4.

Next, on the second main surface (the second surface opposite the firstmain surface on which the n-type silicon carbide layer 1 is formed) ofthe n⁺-type silicon carbide semiconductor substrate 100, the rearelectrode 13 and the rear electrode pad 15 are formed, whereby thesilicon carbide semiconductor Schottky barrier diode depicted in FIG. 1is completed.

FIG. 5 is a graph of surface analysis results of the silicon carbidesemiconductor device according to the first embodiment. In FIG. 5, ahorizontal axis represents depth from the surface of the insulating film9, where up to a dotted line A is in the insulating film 9 and from thedotted line A is in the n-type silicon carbide layer 1. Further, avertical axis represents detected amounts of a measured element(atoms/cm³).

For analysis of impurities over the n-type silicon carbide layer 1 fromthe insulating film 9, Time Of Flight Secondary Ion Mass Spectrometry(TOF-SIMS) was used while etching in a depth direction using argon (Ar)was performed. The TOF-SIMS is a technique of irradiating a solid samplewith an ion beam (primary ion), and utilizing time-of-flight differencesto separate by mass, ions (secondary ions) emitted from the surface.

A first conventional example in FIG. 5 is an example of a case where theinsulating film 9 is formed by a deposition method and the insulatingfilm 9 is formed without removing elements (such as fluorine attached tothe surface) by cleaning. Further, a second conventional example in FIG.5 is an example of a case where the insulating film 9 is formed bythermal oxidation and the insulating film 9 is formed without removingelements (such as fluorine attached to the surface) by cleaning. Asdepicted in FIG. 5, in the first and second conventional examples,fluorine from inside the insulating film 9 was detected at a convertedconcentration of 1×10¹⁷ atoms/cm³ or higher. In particular, when theinsulating film 9 was formed by a deposition method (the firstconventional example), fluorine from the interface of the insulatingfilm 9 and the n-type silicon carbide layer 1 was detected at a highconcentration of 1×10¹⁹ atoms/cm³ or more (converted concentration). Incontrast, for the first embodiment in which the process of removingsurface-attached fluorine, etc. by cleaning is introduced, as depictedin FIG. 5, neither fluorine nor chlorine from inside the insulating film9 or from the interface of the insulating film 9 and the n-type siliconcarbide layer 1 was detected, and is assumed to be a concentration(1×10¹⁷ atoms/cm³) below the sensitivity of the TOF-SIMS.

Further, a test in which reverse voltage was continuously applied wasperformed to evaluate the silicon carbide semiconductor devicefabricated according to the first embodiment. Compared to a case inwhich the process of removing elements such as fluorine was notperformed before forming the insulating film 9, the silicon carbidesemiconductor device fabricated according to the first embodiment wasconfirmed to have a low likelihood of leading to destruction.

As described, the silicon carbide semiconductor device according to thefirst embodiment introduces a process of removing surface-attachedfluorine, etc. by cleaning, before the formation of the insulating film.As a result, fluorine and chlorine from inside the insulating film andfrom the interface of the insulating film and the n-type silicon carbidelayer are no longer detected and therefore, do not cause decreases incarrier mobility of the silicon carbide semiconductor device orirregular decreases of the breakdown voltage, whereby it becomespossible to provide a silicon carbide semiconductor device exhibitingfavorable long-term reliability.

From the results of the test in which reverse voltage was continuouslyapplied, the silicon carbide semiconductor device according to the firstembodiment suppressed device destruction when reverse voltage wasapplied. Further, a device having a low ON resistance may be obtained,which is a characteristic of a silicon carbide semiconductor device.

A second embodiment will be described taking, as an example, adouble-implant MOSFET (DI-MOSFET) fabricated by a double implant (DI)process of respectively forming a p-type well region and an n-typesource region by ion implantation. FIG. 6 is a cross-sectional view ofthe silicon carbide semiconductor device according to the secondembodiment.

As depicted in FIG. 6, in the silicon carbide semiconductor deviceaccording to the second embodiment, the n-type silicon carbide layer 1is provided on the first main surface, for example, a (0001) plane (Siface), of the n⁺-type silicon carbide semiconductor substrate 100. Inthe first main surface (the first surface of the n-type silicon carbidelayer 1 opposite the second surface thereof facing the n⁺-type siliconcarbide semiconductor substrate 100) of the n-type silicon carbide layer1, the p-type ion implant layer ((p-type base region), (second siliconcarbide layer of a second conductivity type)) 4 is selectively provided.In the p-type ion implant layer 4, an n⁺-type source region 7 and ap⁺⁺-type contact region 8 are selectively provided. Further, in an outerperiphery of the device, an edge termination structure region (notdepicted) is provided.

On the surface of the n-type silicon carbide layer 1, the insulatingfilm 9 (gate insulating film) is provided. By a method similar to themethod of the first embodiment, impurities are removed and therefore,neither fluorine nor chlorine is detected from inside the insulatingfilm 9, or from the boundary layer of the insulating film 9 and then-type silicon carbide layer 1, or from the surface of the n-typesilicon carbide layer 1 where the insulating film 9 is provided.

Further, a gate electrode 10 is provided in a region spanning betweenadjacent p-type ion implant layers 4, and an interlayer insulating film11 is provided on the gate electrode 10, the n⁺-type source region 7,and the p-type ion implant layers 4. An opening of the interlayerinsulating film 11 is provided on the n⁺-type source region 7 and thep⁺⁺-type contact region 8. An opening of the interlayer insulating film11 is further provided in a junction (not depicted) of the gateelectrode 10 and the electrode pad 14.

In the opening of the interlayer insulating film 11, the contactelectrode 12 is provided on the n⁺-type source region 7 and the p⁺⁺-typecontact region 8. The electrode pad 14 is provided so as to cover thecontact electrode 12. Further, the electrode pad 14 is further providedon a junction of the gate electrode 10 and the electrode pad 14, andvoltage is applied separated to the contact electrode 12 and the gateelectrode 10. On the rear surface of the n⁺-type silicon carbidesemiconductor substrate 100, the rear electrode (drain electrode) 13 andthe rear electrode pad 15 are provided.

The method of manufacturing a silicon carbide semiconductor deviceaccording to the second embodiment will be described taking, as anexample, a case in which a DI-MOSFET is fabricated. FIGS. 7, 8, and 9are cross-sectional views of the silicon carbide semiconductor deviceaccording to the second embodiment during manufacture. First, then⁺-type silicon carbide semiconductor substrate 100 doped with nitrogenis prepared. Next, the n-type silicon carbide layer 1 doped withnitrogen is formed on the n⁺-type silicon carbide semiconductorsubstrate 100 by epitaxial growth.

Next, an oxide film mask for ion implantation is formed byphotolithography and etching, and the p-type ion implant layer 4 isselectively formed in the surface layer of the n-type silicon carbidelayer 1 by ion implantation. Next, an oxide film mask for ionimplantation is formed by photolithography and etching, and the n⁺-typesource region 7 and the p⁺⁺-type contact region 8 are selectively formedin the surface layer of the p-type ion implant layer 4 by ionimplantation. In the ion implantation, the n-type region is formed byimplanting phosphorus ions or nitrogen ions, and the p-type region isformed by implanting aluminum ions. Further, in an outer periphery ofthe device, the edge termination structure region (not depicted) isformed. The structure formed up to here is depicted in FIG. 7.

Next, after the ion implantation mask is removed, activation annealingis performed at a temperature of about 1700 degrees C. in an inertatmosphere containing, for example, argon. Next, a sacrificial oxidefilm (not depicted) is formed and the sacrificial oxide film is removedby hydrofluoric acid, whereby a damage layer and impurities such asmetal on the surface of the n-type silicon carbide layer 1 are removed.Subsequently, the RCA cleaning is performed and thereafter, by a methodsimilar to the method of the first embodiment, silicon carbide surfaceimpurities are removed, and the insulating film 9 is grown by thermaloxidation on the surface of the n-type silicon carbide layer 1. Thestructure formed up to here is depicted in FIG. 8.

Next, a poly-silicon film is formed by chemical vapor deposition (CVD),and by a photolithography process, the gate electrode 10 is formed inthe region spanning between adjacent p-type ion implant layers 4.Although a silicon oxide film pattern may be formed in advance in aregion not requiring the insulating film 9 such as on the edgetermination structure region, etc., in such cases as well, similarly asdescribed above, before the silicon oxide film is formed, the process ofremoving impurities is performed.

Next, the interlayer insulating film 11 constituting the silicon oxidefilm is formed by CVD, and the opening of the interlayer insulating film11 is formed on the n⁺-type source region 7 and the p⁺⁺-type contactregion 8 by photolithography. Further, the opening of the interlayerinsulating film 11 is further formed at the junction (not depicted) ofthe gate electrode 10 and the electrode pad 14.

Next, a Ni film, etc. is formed by sputtering, and a pattern is formedon the n⁺-type source region 7 and the p⁺⁺-type contact region 8 by aphotolithography process. The Ni film, etc. is heated by rapid thermalannealing (RTA) at a temperature of about 1000 degrees C. in an inertgas atmosphere or a reduced-pressure atmosphere, forming the contactelectrode 12. The structure formed up to here is depicted in FIG. 9.

Next, the electrode pad 14 containing Al and having a thickness of about5 μm is formed so as to cover the contact electrode 12. The electrodepad 14 is further formed on the junction of the gate electrode 10 andthe electrode pad 14, and voltage is applied separately to the contactelectrode 12 and the gate electrode 10. On the rear surface of then⁺-type silicon carbide semiconductor substrate 100, the rear electrode(drain electrode) 13 and the rear electrode pad 15 are formed, wherebythe silicon carbide semiconductor device (DIMOSFET) depicted in FIG. 6is formed.

To evaluate the silicon carbide semiconductor device fabricatedaccording to the second embodiment, forward ON resistance was evaluated.Compared to a case in which the process of removing elements such asfluorine was not performed before forming the insulating film 9, thesilicon carbide semiconductor device fabricated according to the secondembodiment was confirmed to have a low likelihood of leading todestruction.

As described, the semiconductor device according to the secondembodiment, similarly to the first embodiment, introduces a process ofremoving surface-attached fluorine, etc. by cleaning, before theformation of the insulating film. As a result, effects similar to thoseof the first embodiment are obtained. Further, since silicon carbidesurface impurities are removed, it becomes possible to reduce theforward ON resistance.

A third embodiment will be described taking, as an example, a siliconcarbide semiconductor device having a trench structure. FIG. 10 is across-sectional view of the silicon carbide semiconductor deviceaccording to the third embodiment.

As depicted in FIG. 10, in the silicon carbide semiconductor deviceaccording to the third embodiment, the n-type silicon carbide layer 1(first n-type silicon carbide layer) is provided on the first mainsurface, for example, a (0001) plane (Si face), of the n⁺-type siliconcarbide semiconductor substrate 100. The n⁺-type silicon carbidesemiconductor substrate 100 is a silicon carbide single-crystalsubstrate doped with an n-type impurity such as nitrogen. The n-typesilicon carbide layer 1 is a low-concentration n-type drift layer dopedwith an n-type impurity such as nitrogen. An impurity concentration ofthe n-type silicon carbide layer 1 is lower than an impurityconcentration of the n⁺-type silicon carbide semiconductor substrate100. A thickness of the n-type silicon carbide layer 1 varies accordingto the device breakdown voltage and a thickness from about 3 μm to 100μm is used.

In the first main surface (the first surface of the n-type siliconcarbide layer 1 opposite the second surface thereof facing the n⁺-typesilicon carbide semiconductor substrate 100 of the n-type siliconcarbide layer 1), a second n-type silicon carbide layer 2 is provided.The second n-type silicon carbide layer 2 is a low-concentration n-typedrift layer. An impurity concentration of the second n-type siliconcarbide layer 2 is equal to the impurity concentration of the n-typesilicon carbide layer 1 and therefore, is doped with an n-type impuritysuch as nitrogen. A thickness of the second n-type silicon carbide layer2 may be a thickness sufficient to become a current path and a thicknessof about 0.3 μm to 0.7 μm is used.

In the n-type silicon carbide layer 1 and the second n-type siliconcarbide layer 2, the p-type ion implant layer (p⁺-type base region) 4 isprovided. In the n-type silicon carbide layer 1, a p⁺-type ion implantregion 5 positioned at a bottom of a trench 20 described hereinafter isformed. Further, in a region constituting a current path of a peripheryof the p-type ion implant layer 4 and the p⁺-type ion implant region 5,an n-type ion implantation layer 6 may be provided. An impurityconcentration of the n-type ion implantation layer 6 is lower than theimpurity concentration of the n⁺-type silicon carbide semiconductorsubstrate 100 and higher than the impurity concentration of the n-typesilicon carbide layer 1.

On a first main surface (first surface of the second n-type siliconcarbide layer 2 opposite a second surface thereof, the second surfacefacing toward the n⁺-type silicon carbide semiconductor substrate 100)of the second n-type silicon carbide layer 2, a p-type silicon carbidelayer (third silicon carbide layer of the second conductivity) 3 isprovided. The p-type silicon carbide layer 3 is, for example, a p-typelayer doped with aluminum (Al) and provided to have a thickness of about0.5 μm to 2.0 μm. The p-type silicon carbide layer 3 functions as achannel of the trench-type MOSFET.

On a first main surface of the p-type silicon carbide layer 3, then⁺-type source region 7 and the p⁺⁺-type contact region 8 are provided.The n⁺-type source region 7 and the p⁺⁺-type contact region 8 are incontact with each other. Further, the trench 20 is provided in thep-type silicon carbide layer 3. The trench 20 reaches at least thesecond n-type silicon carbide layer 2 from a first main surface (a firstsurface of the p-type silicon carbide layer 3 opposite a second surfacethereof, the second surface facing toward the n⁺-type silicon carbidesemiconductor substrate 100) of the p-type silicon carbide layer 3.Further, the bottom of the trench 20 is in contact with the p⁺-type ionimplant region 5 formed in the n-type silicon carbide layer 1, or isnear the p⁺-type ion implant region 5. The bottom and a side surface ofthe trench 20 may have a continuous, curved surface formed by anannealing method, whereby local concentrations of electric field may besuppressed.

The insulating film 9 (gate insulating film) is provided along a surfaceof the trench 20. By a method similar to the method of the firstembodiment, impurities are removed and therefore, neither fluorine norchlorine is detected from inside the insulating film 9, or from aboundary layer of the insulating film 9 and the second n-type siliconcarbide layer 2, or from the surface of the second n-type siliconcarbide layer 2 where the insulating film 9 is provided. Further, thegate electrode 10, which is insulated from the periphery by theinsulating film 9, is provided in the trench 20. A part of the gateelectrode 10 may protrude outside the trench 20.

The interlayer insulating film 11 is provided so as to cover the gateelectrode 10 embedded in the trench 20, on the entire first main surfaceside of the p-type silicon carbide layer 3. A contact electrode (sourceelectrode) 12 that is in contact with the n⁺-type source region 7 andthe p⁺⁺-type contact region 8 via a contact hole opened in theinterlayer insulating film 11 is provided. The contact electrode 12 iselectrically insulated from the gate electrode 10 by the interlayerinsulating film 11. The electrode pad 14 is provided on the contactelectrode 12.

On the second main surface (the second surface opposite the first mainsurface on which the n-type silicon carbide layer 1 is formed) of then⁺-type silicon carbide semiconductor substrate 100, the rear electrode(drain electrode) 13 and the rear electrode pad (drain electrode pad) 15are provided.

The method of manufacturing a silicon carbide semiconductor deviceaccording to the third embodiment will be described, taking as anexample, a case in which trench-type silicon carbide semiconductordevice is fabricated. FIGS. 11, 12, 13, 14, and 15 are cross-sectionalviews of the silicon carbide semiconductor device according to the thirdembodiment during manufacture. First, the n⁺-type silicon carbidesemiconductor substrate 100 doped with nitrogen is prepared. Next, then-type silicon carbide layer 1 doped with nitrogen is formed on then⁺-type silicon carbide semiconductor substrate 100 by epitaxial growth.

Next, in the first main surface (the first surface of the n-type siliconcarbide layer 1 opposite the second surface thereof facing the n⁺-typesilicon carbide semiconductor substrate 100) of the n-type siliconcarbide layer 1, a lower p⁺-type base region 4 a constituting the p-typeion implant layer 4 and the p⁺-type ion implant region 5 positioned atthe bottom of the trench 20 are formed. Ion implantation depths of thelower p⁺-type base region 4 a and the p⁺-type ion implant region 5 maybe at maximum about 0.7 μm, which enables recovery of crystal defects byheat treatment. The impurity concentrations of the lower p⁺-type baseregion 4 a and the p⁺-type ion implant region 5 is formed to be about5×10¹⁷ to 1×10¹⁹/cm³. Next, in a region constituting a current path of aperiphery of the lower p⁺-type base region 4 a and the p⁺-type ionimplant region 5, a lower n-type ion implantation layer 6 a is formed.An impurity concentration of the lower n-type ion implantation layer 6 ais lower than the impurity concentration of the n⁺-type silicon carbidesemiconductor substrate 100 and higher than the impurity concentrationof the n-type silicon carbide layer 1. The structure formed up to hereis depicted in FIG. 11.

On the first main surface (the first surface of the n-type siliconcarbide layer 1 opposite the second surface thereof facing the n⁺-typesilicon carbide semiconductor substrate 100) of the n-type siliconcarbide layer 1, the second n-type silicon carbide layer 2 is formed.Next, in the first main surface (the first surface of the second n-typesilicon carbide layer 2 opposite the second surface thereof facingtoward the n⁺-type silicon carbide semiconductor substrate 100) of thesecond n-type silicon carbide layer 2, an upper p⁺-type base region 4 bis formed in a region continuous with the lower p⁺-type base region 4 aformed in the n-type silicon carbide layer 1. The region formed by thelower p⁺-type base region 4 a and the upper p⁺-type base region 4 b isindicated as the p-type ion implant layer 4. Here, an impurityconcentration of the upper p⁺-type base region 4 b is formed to be about5×10¹⁷ to 1×10¹⁹/cm³, equal to the impurity concentration of the lowerp⁺-type base region 4 a.

Next, an upper n-type ion implantation layer 6 b may be formed in a partthat constitutes the current path of the periphery of the p-type ionimplant layer 4 and that is in contact with the lower n-type ionimplantation layer 6 a formed on the n-type silicon carbide layer 1. Animpurity concentration of the upper n-type ion implantation layer 6 b islower than the impurity concentration of the n⁺-type silicon carbidesemiconductor substrate 100 and higher than the impurity concentrationof the n-type silicon carbide layer 1. The region formed by the lowern-type ion implantation layer 6 a and the upper n-type ion implantationlayer 6 b is indicated as the n-type ion implantation layer 6. Thestructure formed up to here is depicted in FIG. 12.

Next, on the first main surface (the first surface of the second n-typesilicon carbide layer 2 opposite the second surface thereof facingtoward the n⁺-type silicon carbide semiconductor substrate 100) of thesecond n-type silicon carbide layer 2, the p-type silicon carbide layer3 is formed. The p-type silicon carbide layer 3 is formed by doping, forexample, aluminum (Al) to about 5×10¹⁶ to 1×10¹⁸/cm³. Next, in the firstmain surface of the p-type silicon carbide layer 3, the n⁺-type sourceregion 7 and the p⁺⁺-type contact region 8 are formed so as to be incontact with each other. The structure formed up to here is depicted inFIG. 13.

Next, the trench 20 is formed to reach at least the second n-typesilicon carbide layer 2 from a first main surface (first surface of thep-type silicon carbide layer 3 opposite a second surface thereof, thesecond surface facing toward the n⁺-type silicon carbide semiconductorsubstrate 100) of the p-type silicon carbide layer 3. Next, asacrificial oxide film (not depicted) is formed and the sacrificialoxide film is removed by hydrofluoric acid, whereby a damage layer andimpurities such as metal on the trench surface are removed.Subsequently, after the RCA cleaning is performed, silicon carbidesurface impurities are removed by a method similar to the method of thefirst embodiment.

Next, the insulating film 9 is formed along the surface of the trench 20by a deposition method. Next, the gate electrode 10, which is insulatedfrom the periphery by the insulating film 9, is formed in the trench 20.A part of the gate electrode 10 may protrude outside the trench 20. Thestructure formed up to here is depicted in FIG. 14.

Next, the interlayer insulating film 11 is formed so as to cover thegate electrode 10 embedded in the trench 20, on the entire first mainsurface side of the p-type silicon carbide layer 3. Next, the contactelectrode (source electrode) 12 that is in contact with the n⁺-typesource region 7 and the p⁺⁺-type contact region 8 via a contact holeopened in the interlayer insulating film 11 is formed. Next, theelectrode pad 14 is formed on the contact electrode 12. The structureformed up to here is depicted in FIG. 15.

Next, on the second main surface (the second surface opposite the firstmain surface on which the n-type silicon carbide layer 1 is formed) ofthe n⁺-type silicon carbide semiconductor substrate 100, the rearelectrode (drain electrode) 13 and the rear electrode pad (drainelectrode pad) 15 are formed, whereby the trench-type silicon carbidesemiconductor device depicted in FIG. 10 is completed.

To evaluate the silicon carbide semiconductor device fabricatedaccording to the third embodiment, forward ON resistance at a currentvalue of 25 mA was evaluated. The results are depicted in Table 2.

TABLE 2 PREPROCESSING METHOD ON RESISTANCE NONE 1 LOW PRESSUREATMOSPHERE 0.95 800° C. 30 MIN. HYDROGEN ATMOSPHERE 0.90 800° C. 30 MIN.HYDROGEN/SILANE MIXED GAS 0.85 ATMOSPHERE 1400° C. 30 MIN.

As depicted in Table 2, the device ON resistance is assumed to be 1 in acase where the process of removing elements such as fluorine is notperformed before the formation of the insulating film 9. Here, it wasconfirmed the silicon carbide semiconductor device fabricated byperforming the preprocessing as in the second embodiment, etc. tended tohave a lower ON resistance.

As described, the semiconductor device according to the third embodimentintroduces a process of removing surface-attached fluorine, etc. bycleaning, before the formation of the insulating film. As a result,effects similar to those of the first embodiment are obtained. Further,since silicon carbide surface impurities are removed, it becomespossible to reduce the forward ON resistance. In addition, in the thirdembodiment, since the device has a trench structure, a device having alow ON resistance may be realized.

The present invention may be variously modified within a scope notdeviating from the spirit of the invention. For example, in theembodiments above, dimensions, impurity concentrations, etc. may bevariously set according to required specifications. For example, in theembodiments, although an example is described taking a case in which amain surface of the silicon carbide semiconductor substrate containingsilicon carbide is a (0001) plane and on the (0001) plane, a MOS isconfigured, without limitation hereto, by changing the method ofmanufacture, various changes are possible such as the wide bandgapsemiconductor material, the orientation of the substrate main surface,etc. Further, in the embodiments above, although an example is describedtaking a case in which silicon carbide is used as a wide bandgapsemiconductor material, a wide bandgap semiconductor material other thansilicon carbide such as, for example, gallium nitride (GaN) or the likemay be used. Further, in the embodiments above, although the firstconductivity type is an n-type and the second conductivity type is ap-type, the present invention is similarly implemented when the firstconductivity type is a p-type and the second conductivity type is ann-type.

As described, according to the embodiments of the invention, the processof removing surface-attached fluorine, etc. by cleaning, is introducedbefore the formation of the insulating film. As a result, fluorine andchlorine are no longer detected from inside the insulating film, or fromthe interface of the insulating film and the n-type silicon carbidelayer (first silicon carbide layer of the first conductivity type) andtherefore, do not cause decreases in carrier mobility of the siliconcarbide semiconductor device or irregular decreases of the breakdownvoltage, whereby it becomes possible to provide a silicon carbidesemiconductor device exhibiting favorable long-term reliability.

The silicon carbide semiconductor device and the method of manufacturinga silicon carbide semiconductor device according the present inventionachieve an effect in that impurities are suppressed from being mixed inthe channel region, enabling stabilization of the breakdown voltagewithout decreases in carrier mobility.

As described, the silicon carbide semiconductor device and the method ofmanufacturing a silicon carbide semiconductor device according to thepresent invention are useful for high-voltage semiconductor devices usedin power converting equipment and in power supply devices such as invarious industrial machines.

Although the invention has been described with respect to a specificembodiment for a complete and clear disclosure, the appended claims arenot to be thus limited but are to be construed as embodying allmodifications and alternative constructions that may occur to oneskilled in the art which fairly fall within the basic teaching hereinset forth.

What is claimed is:
 1. A method of manufacturing a silicon carbidesemiconductor device, the method comprising: forming a first siliconcarbide layer of a first conductivity type on a front surface of asilicon carbide semiconductor substrate; forming a thermal oxidationfilm on a surface of a base body including the first silicon carbidelayer; removing the thermal oxidation film by a solution containinghydrofluoric acid; washing the base body with a mixture of ammonia waterand a hydrogen peroxide solution, a mixture of hydrochloric acid and ahydrogen peroxide solution, and a dilute hydrofluoric acid; holding thebase body at a temperature of 700 degrees C. to 1000 degrees C. in areduced-pressure atmosphere; and depositing an insulating film on thebase body.
 2. A method of manufacturing a silicon carbide semiconductordevice, the method comprising: forming a first silicon carbide layer ofa first conductivity type on a front surface of a silicon carbidesemiconductor substrate; forming a thermal oxidation film on a surfaceof a base body including the first silicon carbide layer; removing thethermal oxidation film by a solution containing hydrofluoric acid;washing the base body with a mixture of ammonia water and a hydrogenperoxide solution, a mixture of hydrochloric acid and a hydrogenperoxide solution, and a dilute hydrofluoric acid; holding the base bodyat a temperature of 700 degrees C. to 1000 degrees C. in a hydrogenatmosphere; and depositing an insulating film on the base body.
 3. Amethod of manufacturing a silicon carbide semiconductor device, themethod comprising: forming a first silicon carbide layer of a firstconductivity type on a front surface of a silicon carbide semiconductorsubstrate; forming a thermal oxidation film on a surface of a base bodyincluding the first silicon carbide layer; removing the thermaloxidation film by a solution containing hydrofluoric acid; washing thebase body with a mixture of ammonia water and a hydrogen peroxidesolution, a mixture of hydrochloric acid and a hydrogen peroxidesolution, and a dilute hydrofluoric acid; holding the base body attemperature of 700 degrees C. to 1700 degrees C. in a mixed gasatmosphere containing hydrogen and silane; and depositing an insulatingfilm on the base body.